Reaction products of aldehydes and triazine derivatives



Patented Jan. 8, 1946 REACTION PRODUCTS F ALDEHYDES AND IAZIN E DERIVATIVES Gaetano F. D'Alelio and James W. Underwood, Pittsflelrl, Mass asslgncrs to General Electric IN-n8. a corporation of New York No Drawing. Application August 19, 1842, Serial No. 455,356

22 Claims.

This invention relates to the production of new synthetic materials and especially to new reaction products 0!. particular utility in the plastics and coating arts. Specifically the invention is concerned with compositions of matter comprising a. condensation product of ingredients comprising an aldehyde, including polymeric aldehydes, hydroxyaldehydes and aldehyde-addition products, e. g., formaldehyde, paraiormaldehyde, aldol, glucose, dimethylol urea, trimethylol melamine, etc., and a triazine derivative corresponding to the following general formula:

In the above formula 11 represents an integer and is at least 1 and not more than 3, R represents a member of the class consisting of hydrogen and monovalent hydrocarbon and substituted hydrocarbon radicals, more particularl halohydrocarbon radicals, and It represents a member of the class consisting of monovalent aliphatic hydrocarbon radicals and monovalent aromatic and nuclearly substituted, specifically nuciearly halogenated, aromatic hydrocarbon radicals. From the above formula it will be noted that when n is 3 there will be no N HR groups attached to the triazine nucleus.

Illustrative examples of radicals that R in the above formula may represent are: aliphatic (e. g., methyl, ethyl, propyl, isopropyl, butyl, secondary butyl, isobutyl, butenyl, amyl, isoamyl, hexyl, octyl, methallyl, crotyl, etc.), including cycloaliphatic (e. g., cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl, cycloheptyl, etc.) aryl (e. g., phenyl, diphenyl or xenyl, naphthyl, anthracyl, etc); aliphatic-substituted aryl (e. 3., tolyi, xylyl, ethylphenyl, propylphenyl, isopropylphenyl, ailylphenyl, 2-butenylphenyl, propenylphenyl, tertiary-butylphenyl, methylnaphthyl, etc.); aryl-substituted aliphatic (e. g., benzyl, cinnamyl, phenylethyl, phenylpropyl, etc.) and their homologues, as well as those groups with one or more of their hydrogen atoms substituted by. for example. a halogen, more particularly chlorine, bromine, fluorine or iodine. Specific examples or halogeno-substituted hydrocarbon radicals that R. in the above formula may represent are: chloromethyl, chloroethyl, chlorophenyl. dichlorophenyl, ethyl chlorophenyl, chlorocyclohexyl, phenyl chloroethyl, bromoethyl, bromopropyl, fluorophenyl, iodophenyl, bromotolyl; etc. 1

Preferably R is hydrogen.

Illustrative examples of monovalent aliphatic and aromatic hydrocarbon radicals that R in the above formula may represent are radicals such as above mentioned with reference to R. Illustrative examples of monovalent, nuclearly substituted, specifically nuclearly halogenated, aromatlc hydrocarbon radicals that R also may represent are: chlorophenyl, dichlorophenyl, bromophenyl, dibromophenyl, iodcphenyl, fluorcphenyl, chlorotclyl, bromotclyl, chloroxylyl, chloronaphthyl, dichloronaphthyl, chloroxenyl, dichloroxenyl, bromoxenyl and the like. Preferably It represents a lower alkyl radical or a phenyl radical,

Instead of the symmetrical trlazines (s-triazines) represented by Formula I, corresponding derivatives of the asymmetrical triazines or of the vicinal triazines may be used.

The triazine derivatives that are used in carrying the present invention into effect are more fully described and are specifically claimed in our copending application Serial No. 455,357, filed concurrently herewith and assigned to the same assignee as the present invention. More specific examples oi triazine derivatives that may be employed in producing our new condensation products are the tri-(acylhydrazino) s-triazines, the di-(acylhydrazino) amino (-NHR) s-triazines and the carboacylhydrazino diamlno [(NHR) :l s-triazines. As pointed out in copending application Serial No. 455,357, a. method of preparing the triazine derivatives used in carrying the present invention into eflect comprises effecting reaction in the presence oi a hydrohalide acceptor, e. g., a tertiary base such as a trialkyl or a triaryl amine, between (1) a hydrazino triazine corresponding to the general formula.

I 0 f 1 (BEN M L Nil-NR1)- where n and R have the same meanings as given above with reference to Formula I, and (2) a compound corresponding to the general formula 0 .JHLW

where X represents a halogen atom, and n and R have the same meanings as given above with reference to Formula I,

Other examples of triazine derivatives embraced by Formula I that may be employed in practicing our invention are listed below:

Acetylhydrazino diamino s-triazine Di-(acetylhydrazino) amino s-triazine Trilacetylhydrazinoi s-triazine Acetylhydrazino di-(methylamino) s-triazine Propionylhydrazino diamino s-triazine Butyrylhydrazino diamino s-triazine Di-(butyrylhydrazino) amino s-triazine 'iri- (butyrylhydrazlno) s-triazine Vaierylhydrazino diamino s-triazine Di-(valerylhydrazino) amino s-triazine 'Ifl-ivalerylhydrazino) s-triazine Butyrylhydrazino di- (methylamino) s-triazine Valerylhydrazino di- (ethiilamino) s-triazine Bennoylhydrazino di-(aliylamino) s-triazine Chlorobenzoylhydrazino di- (methylamino) s-triazine Propionylhydrazino dl- (chloroethylamino) s-triazine Butyrylhydrazino di- (bromcanilino) s-triazine Di-(propinnylhydrazino) hexylamino s-triazine Tri-(bromobenzoylhydrazino) s-triazlne Acetyihydrazino di- (ethylamino) s-triazine Pronionylhydraz no di- (methylamino) s-triazine Propenoylhydrazino diamino s-triazine Di-(propionylhydrazino) amino s-trlazine Tri-ipronionylhydrazino) s-triaz ne Di- (proplonylhydrazino) methylamino s-triazine Acetylhydraz no di- (butylamino) s-triazine Acetylhydrazino di-(propenylamino) s-triazine Propionylhydrazino di-(cyclohexylamino) s-triazine Aeetylhydrazino dianilino s-triaz ne Acetylhyrlraz no ditnluido s-triazine Acetylhyclrazino dixylidino .s-triazine Acetyihydrsz no di-(phenethylamino) s-triazine Di-(acetylhydrazino) aniline s-triazlne Di- (acetylhydrazino) toluido s-triazine Di- (acetylhydrazino) xylidino s-triaz ne Acetylhydrazino di-(ethylanii no) s-triazlne Acetylhydrazino di-ichloroaniiinol s-triaxine Acetylhydrazino di-(benzylamino) s-triazine z-acetylhydrazino 4-methylamino B-amino s-triazine (4-acetylhydrazino 2-methylamino 8- amino s-triazine; d-acetylhydrazino z-methylamino 4-amino s-triazine) z-acetylhydrazino i-anilino G-amino s-triazine z-acetylhydrazino 4-anilino G-mcthylamino s-triazine Benzoylhydrazino diamino s-triazine Chlorobenzoylhydrazino diamino s-triazine Di- (benzoylhydrazino) amino s-triazine Trl-(benzoylhydrazino) s-triazine Toluylhydrazino diamino s-triazine Di-(toluylhydrazino) amino s-trlazine Tri-(toluylhydrazino) s-triazine Dimethylbenzoylhydrazino diamino s-triazine Chiorobenzoylhydrazino di-(chloroethylamino) s-triazine Di-(benzoylhydrazino) methylamino s-triazine Di-(acetylhydrazino) benzoylhydramno s-triazine Di-(acetylhydrazino) propionylhydrazino s-triasine Z-acetylhydrazino 4-benzoylhydrazino d-propionylhydrazino s-triazine Acetylhydrazino di-(fluoroanilino) s-triazine Propionylhydrazlno di- (iodoanilino) s-triazine Benzoylhydrazino di- (bromotoluido) s-triazine Bromobenzoylhydraaino di- (bromoanilino) s-trlazine Acetylbydrazino di- (chlorotoluido) s-triazine Acetylhydrazino di-(wclohexylamino) s-triazine Acetylhydrazino di-(octylamino) s-triazine Acetylhydrazino di-(cyclohexenylamino) s-triazine Acetylhydrazino di-(allylamino) s-triazine Di-(propionylhydrazino) methallylamino s-triazine The present invention is based on our discovery that new and valuable materials of particular utility in the plastics and coating arts can be produced by eii'ecting reaction between ingredients comprising essentially an aldehyde. including polymeric aldehydes, hydroxyaldehydes and aldehyde-addition products, and a triazine derivative of the kind embraced by Formula I, numerous examples of which have been given above and in our copending application Serial No. 455,357.

In the production of molded articles from molding compositions comprising a filled or unfilled thermosetting resin, it is highly desirable that the molding compound have a high plastic flow during molding combined with a rapid cure to an insoluble and infusible state. Surprisingly it was found that the heat-curable resinous condensation products of this invention and molding compositions made therefrom show excellent flow characteristics during a short curing cycle. The molded articles have a high dielectric strength and a very good resistance to arcing. They have a good surface finish and excellent resistance to water, being better, in general, than the ordinary urea-formaldehyde resins in this respect. This was quite surprising and unexpected and in no way could have been predicted. The cured resins of the present invention also have a high resistance to heat and abrasion and, therefore. are especially suitable for use where optimum heatand abrasion-resistance are properties of primary importance.

Resins heretofore have been made by condensing an aldehyde with an aminotriazine, e. g., melamine. The suggestion also has been made that resinous materials be prepared by condensl ing an aliphatic aldehyde containing a. chain of at the most six carbon atoms with compounds of the general formula wherein x stands for a member oi the group consisting of hydrogen and the amino (NH:) radical, and R represents a member of the class consisting of hydrazino, phenyl, hydroxy, aikoxy and thioether groups and halogen atoms. Such resins generally have excellent heat and are resistance, but are deficient in other properties that are desirable in a resin to be used in the production or molding compositions and molded articles. For example. the high basicity of cyaniu'trihydrazide, which is embraced by Formula II, imparts to resins prepared therefrom, and to articles molded from molding compounds made from such resins. unsatisfactory curing characteristics and a poorer resistance to aqueous solvents (particularly aqueous solvents containing acidic materials) than many applications require. Furthermore, the plasticity during molding often is unsatisfactory. These and other disadvantages in the materials of this class heretofore known intheresinartareavoidedbyusingasastartin: reactant a triazine derivative wherein at least one or the substituent groupings attached to the carbon atoms of the triasine nucleus is a carboacylhydraaino grouping.

In practicins our invention the initial condensation reaction may be carried out at normal or at elevated temperatures. at .atmospheric, sub-atmospheric or super-atmospheric pressures, and under neutral, alkaline or acid conditions. Preferably the reaction between the components is initiated under alkaline conditions. Any substance yielding an alkaline or an acid aqueous solution may be used in obtaining alkaline or acid conditions for the initial condensation reaction. For example. we may use an alkaline substance such as sodium, potassium or calcium hydroxides, sodium or potassium carbonates, mono-, dlor trl-amines. etc. In some cases it is desirable to cause the initialcondensation reaction between the components to take place in the presence 01' a primary condensation catalyst and a secondary condensation catalyst. The primary catalyst advantageously is either an aldehyde non reactable nitrogen containing basic tertiary compound, e. g., tertiary amines such as trialkyl (e. g., trimethyl, triethyl, etc.) amines, triaryl (e. g., triphenyi, tritolyl, etc.) amines, etc., or an aldehyde-reactable nitrogencontaining basic compound, for instance ammonia, primary amines (e. g., ethyl amine, propyl amine, etc.) and secondary amines (e. g., dipropyl amine, dibutyl amine, etc.) The secondary condensation catalyst, which ordinarily is used in an amount less than the amount of the primary catalyst, advantageously is a fixed alkali, for instance a, carbonate, cyanide or hydroxide of an alkali metal (e. g., sodium, potassium, lithium, etc.).

Illustrative examples of acid condensation catalysts that may be employed are inorganic or organic acids such as hydrochloric, sulfuric, phosphoric, acetic, lactic, acrylic, malonic, etc., or acid salts such as sodium acid sulfate, monosodium phosphate, monosodium phthalate, etc. Mixtures of acids, acid salts or of acids and of acid salts may be employed if desired.

The reaction between the aldehyde, e. g., formaldehyde, and the triazine derivative may be carried out in the presence or absence of solvents or diluents, fillers, other natural or synthetic resinous bodies, or while admixed with other materials that also can react with the aldehydic reactant or with the triazine derivative, e. g., urea (NI-I2CONH2) thiourea, selenourea and iminourea (guanidine), substituted ureas, thicureas, selenoureas and iminoureas. more particularly urea derivatives such as mentioned, for example, in D'Alelio Patent No. 2,285,418, page 1, column 1, lines 41-49; monoamides of monocarboxylic acids and polyamides of polyearhoxylic acids, e. g., acetamide, halogenated acetamides (e. g., a chlorinated acetamide), maleic monoamide, malonic monoamide, phthalic monoamide, maleic diamide, fumaric diamide, malonic diamide. itaconic dlamide, succinic diamide, phthalic diamide. th monoamide, diamide and triamide of tricarballylic acid, etc.; aminodiazines; aldehyde-reactalole triazines other than the triazine derivatives constituting the primary components or the resins of the present invention, e. g., melamine, ammeiine, ammelide, melem, melam. melon, numerous other examples being given in various copending applications or one or both of us, for instance in DAlelio copending application Serial No. 377,524, filed February 5, 1941,

and in applications reierred to in said copending application; P1181101 and" substituted henols. e. g., the cresols, the xylenols, the tertiary alkyl phenols and other phenols such as mentioned, for example, in DAielio Patent 2,239,441; monohydric and polyhydric alcohols, e. g., butyl alcohol. heptyl alcohol, amyl alcohol, octyl alcohol, 2- ethylbutyl alcohol, ethylene glycol, propylene glycol, glycerine. p lyvinyl alcohol, etc.; amines, including aromatic amines. e. 8.. aniline, etc; andthe like.

The modifying reactants may be incorporated with the triazine derivative to form an intercondensation product by mixing all the reactants and efl'ecting condensation therebetween or by various permutations of reactants as described. for example, in DAlelio Patent No. 2,285,418 with particular reference to reactions involving a urea, an aliphatic aldehyde and a chlorinated acetamide. For example, we may form a partial condensation product of ingredients comprising (1) urea or melamine or urea and melamine, (2) a triazine derivative of the kind embraced 'by Formula I, for instance acetyihydrazino diamino s-triazine, di-(acetylhydrazino) amino s-triazine, tri-(acetylhydrazino) s-triazine, propionylhydrazino diamino s-triazine, acetylhydrazino di-(methylamino s-triazine, etc., and

(3) an aldehyde, including p ymeric aldehydes, hvdroxyaldehydes and aldehyde-addition products. e. g., formaldehyde, paraformaldehyde, aldol, glyceraldehyde, dimethyloi urea, a polymethylol melamine, e. g., hexamethylol melamine, etc. Thereafter, we may eifect reaction between this partial condensation product and, for example, a curing reactant, specifically a chicrinated acetamide, to obtain a heat-curable composition.

Some of the condensation products of this invention are thermoplastic materials even at an advanced stage oi condensation, while others are thermosetting or potentially thermosetting bodies that convert under heat or under heat and pressure to an insoluble, iniusible state. The thermoplastic condensation products are of particular value as plasticizers for other synthetic resins. The thermosetting or potentially thermosetting resinous condensation products, alone or mixed with fillers, pigments, dyes, lubricants, plasticizers. curing agents, etc., may be used, for example, in the production 01' molding compositions.

The liquid intermediate condensation products of the invention may be concentrated or diluted further by the removal or addition of volatile solvents to form liquid coating compositions of adjusted viscosity and concentration. The heatconvertible or potentially heat-convertible resinous condensation products may be used in liquid state, for instance, as surface-coating materials, in the production of paints, varnishes, lacquers, enamels, etc., for general adhesive applications, in producing laminated articles and for numerous other purposes. The liquid heathardenable or potentially heat-hardenable condensation products also may be used directly as casting resins, while those which are of a gellike nature in partially condensed state may be dried and granulated to form clear, unfilled heat-convertible resins.

In order that those skilled in the art better may understand how the present invention may be carried into effect, the following examples are given by 'way of illustration and not by way of limitation. All parts are by weight.

Example 1 Parts Acetylhydrasino diamino s-trlazine 109.8 Aqueous formaldehyde (approx. 37.1%

HCHO) ..L 194.4 Sodium hydroxide in parts water 0.1 Aqueous ammonia (approx. 28% RBI) 10.0

were heated together under reflux at the boiling temperature of the mass for minutes, yielding a clear. colorless syrup. When a small sample or this syrup was heated on a 140-150 C. hot plate it was converted into an iniusible mass. when the syrupy condensation product was treated with a small amount of chloroacetamide (monochloroacetamide), followed by heating on a. 140' C. hot plate, the curing of the syrup to an insoluble and infusible state was materially accelerated.

One part of chloroacetamide was added to the main portion of the resinous syrup and heating under reflux was continued for an additional 5 minutes. The pH of the syrup at the end of this reaction period was 7.08. This syrupy resin cured rapidly when tested on a 140 C. hot plate. The syrup was divided into-two equal parts. To one portion 01' the syrup was added 40 parts alpha cellulose in flock form and 0.2 part of a mold lubricant. specifically zinc stearate. To the other portion was added 100 parts asbestos and 0.2 part zinc stearate. The wet molding compounds produced in this manner were dried at 65 C. The composition containing the alpha cellulose was dried for 1% hours and the asbestos-containing compound for 3 hours. Samples of the dried and ground molding compositions then were molded at 130 C. under a pressure or 2,000 pounds per square inch. The celiulosic composition was molded for 4 minutes and the asbestos compound for 5 minutes. In both cases well-cured molded pieces were obtained. The molded articles had very good resistance to water as shown by the fact that when the individual sample was immersed in boiling water for 15 minutes, followed by immersion in cold water for 5 minutes, the molded piece containing the cellulosic filler absorbed only 0.27% by weight of water and the one containing the asbestos only 1.18% by weight of water. Both molding compounds showed very good plastic flow during molding.

Instead of using chloroacetamide in accelerating the curing of the potentially reactive resinous material, heat-convertible compositions may be produced by adding to the partial condensation product (in syrupy or other form) direct or active curing catalysts (e. g., citric acid, phthalic anhydride, malonic acid, oxalic acid, etc.) or latent curing catalysts (e. g., sodium chloroacetate. N- diethyl chloroacetamide, glycine ethyl ester hydrochloride, etc). or by intercondensation with curing reactants other than monochloroacet- July 23, 1040. now Patent No. 2,325,375, and 8erial No. 354,395. flied August 27, 1040. now Patent No. 2.325.378. both of which applications issued on July 27. 1943. and are assigned to the some assignee as the present invention.

All of the above ingredients with the exception of the chloroacetamide were heated together under reflux at the boiling temperature of the mass for 30.minutes. The chloroacetamide was now added and heating under reflux was continued for an additional 10 minutes. A molding compound was prepared from the resulting resinous syrup by mixing therewith parts alpha cellulose and 0.2 part zinc steal-ate. The wet molding compound was dried for 2 hours at 05' C. A well-cured molded piece having a good surface finish and a well-hilt and homogeneous structure was obtained by molding a sample 01' the dried and ground molding compound for 6 minutes at 130 C. under a pressure of 2,000 pounds per square inch. The molding composition showed very good plastic flow during midins.

All of the above ingredients with the exception of the chloroacetamide were heated together under reflux at boiling temperature (or 15 minutes. at the end of which period of time the chloroacetamide was added and refluxing was continued for an additional 4 minutes. Forty parts alpha cellulose and 0.2 part zinc stearate were mixed with the resulting resinous syrup to form a molding compound. The wet molding composition was dried at C. for 1% hours. A sample of the dried and ground molding compound was molded for 5 minutes at C. under a pressure of 2,000 pounds per square inch, yielding a well-cured molded piece having a well-knit and homogeneous structure. The molding composition showed excellent plasticity during molding.

Example 4 Parts Aoetylhydrazino diamino s-triazine 30.6 Dimethylol urea (commercial grade containing approx. 11% by weight of water)- 31.0 Sodium hydroxide in 5 parts water 0.1 Aqueous ammonia (approx, 28% 1431)---- 10.0 Chloroacetamide 1.0 Water 120.0

Emmple Paris Acetylhydrasino diamino e-triaslne 04.0 Acrolein 01.2 Sodium hydroxide in 5 parts water 0.1 Water 100.0

wereheatedtogetherunderrefluxattheboilins temperature of the mass for minutes, yielding athicksyrup containinsasmailamountof precipitated resin.

When a small sample of this resin was heated on a 140' 0. hot plate it cured slowly to an infusible mass. The addition of a curins asent such as mentioned under Example 1. ior instance. suliamic acid. slyclne. nitroiuea. etc... accelerated thecureoithereslntotheinsolubleandintusihle state. The resinous composition oi this example maybeusedintheproductionoi moldinscompositionl.

Example 0 Parts licetylhsdrasino diamino s-trissine. 04.0

' Butylalcohol 111.0

Aqueous formaldehyde (approx. 37.1%

ECHO) 07.2 Sodium hydroxide in 5 parts water 0.1

wereheated togetherunderreiluxatthe boiling temperature of the mass ior approximately minutes, yielding a clear, colorless syrup. When a sample of this syrup was heated on a 140' C. hot plate it was converted into a transparent, tough. thermoplastic fllm. The uncured resin was soluble in ethyl alcohol. The syrupy condensation product was potentially heat-curable as evidenced by the fact that when chloroacetamide, citric acid, nitrourea or other curiae agent such as mentioned under Example 1 was incorporated either into the syrup or into the dehydrated resin, followed by heating on a 140 0. hot plate. an insoluble and iniusible resin was obtained. The solubility and film-forming characteristics of the resinous material 01' this example make it particularly suitable for use in the preparation of liquid coating compositions.

Sodium hydroxide in 5 parts water 0.1 were heated together under reflux at boiling temperature for 15 minutes, yielding a clear syrup.

This syrupy condensation product was potentially heat-curable as shown by the fact that when asmentionedundsrli'xamplolwasaddedtothe syrup.ioliowedbyheatinsat140'0.,theresinous material was converted to a cured or insoluble and iniusible state. The piastlcityoithe thermosettins resin durins curinsindioated that the productoithisexamplewouldbesuitableioruse asamodiiier or aminoplasts and other-synthetic resins oi unsatisfactory ilow characteristics to improvetheplasticity thereof.

' Example 8 acetylhydraxino diamino s-triasina..--.....- 60.0

Aqueous formaldehyde (approx. 81.1%

ECHO) 02.2

Giycerine 22.0

Sodium hydroxide in ii parts water 0.1

wereheatedtosetherunderreiluxathoilinstemperatureioro yieldinaathicksyrup thatyelledimon toroomtemperature. Theplasticity andcurins charaotsristicsotthe resinousmaterialotthisexampisweremuch sameastheproduototlxample'l.

Example 0 (approx. 87.1%

ECHO) 97.2

"Sodiumhydroxideintpartswater 0.1

a state when were heated tosether under reflux at boiling temperatureiortminuteayieldinsaselledresin. Thisresinmeltedandthencuredtoaniniusihle asampleoi'itwasheatedona 140C. hot plate. The cured resin was white and had .outstandinxflexibiiityinfllmiorm. Initscured statetheresinwasnotaflectedhysoiventssueh as ethyl alcohol. benzene and Bolvatone. Example 10 Parts Acetylhydrasino diamino s-triaxine 18.8

Polyvinyl aicohol....---..-------------..--- 20.4 Aqueous formaldehyde (approx. 81.1%

ECHO) 48.0 Sodium hydroxide in 5 parts water.----..- 0.1 Water 100.0

wereheatedtocetherunderretluxatthehoilina temperature of the mass for 15 minutes. yielding acleanveryvisooussyrup. Whenasampleot thissyrupwasheatedona140' C.hotplate,it bodied to a thermoplastic resin. When a sample oi'theresin wastreatedwithasmailamount of hydrochloric acid and the resultin: material then heated on a 140' 0. hot plate, a tough, iniusible. water-resistant him was formed. Instead oi hydrochloric acid. other curing agents such as mentioned under Example 1 may be employed to improve the curing characteristics and the water resistance of the resinous material of this example.

It will be understood. of course, by those skilled in the art that the reaction between the aldehyde and the trianne derivative may be eilected at temperatures rousing. for example. from room temperature to the fusion or boiling temperature citric acid. slycine or other curing agent such 70 reflux. the reaction between the components may be carried out at lower temperatures, for example, at temperatures ranging from room temperature to a temperature near the boiling temperature using longer reaction periods and, in some cases, stronger catalysts and higher catalyst concentrations.

It also will be understood by those skilled in the art that our invention is not limited to condensation products obtained by reaction of ingredients comprising an aldehyde and the specific carbo acylhydrazino s-triazine named in the above illustrative examples. Thus, instead 01' acetylhydrazino diamino s-triazine we may use, for example, di-(acetylhydraaino) amino s-triazine, tri-(acetylhydrazino) s-triasine, propionylhydraxino diamino s-triazine, acetylhydrazino di- (methylamino) s-triazine, or any other compound oi the kind embraced by Formula I, numerous examples or which have been given above and in our copending application Serial No. 455,- 357. I

In producing these new condensation products the choice of the aldehyde is dependent largely upon economic considerations and upon the particular properties desired in the finished product. We preter to use as the aldehydic reactant formaldehyde or compounds engendering formaldehyde, e. g., paraformaidehyde, hexamethylene tetramine, etc. Illustrative examples of other aldehydes that may be employed are acetaidehyde, propionaldehyde, butyraldehyde, heptaldehyde, octaldehyde, methacrolein, crotonaldehyde, benzaldehyde, iuriural, hydroxyaldehydes (e. g., aldoi, glucose, glycoliic aldehyde, giyceraldehyde. etc), mixtures thereof, or mixtures of iormaldehyde (or compounds engendering formaldehyde) with such aldehydes. Illustrative examples of aldehyde-addition products that may be used instead o! the aidehydes themselves are the monoand poly-(N-carbinol) derivatives, more particularly the monoand poly-methyiol derivatives of urea, thiourea, selenourea and iminourea, and of substituted ureas, selenoureas, thioureas and iminoureas, monoand poiy-(N-carbinol) derivatives oi amides oi polycarboxylic acids, e. g., maleic, itaconic, fumaric, adipic, malonic, succinic, citric, phthalic, etc., monoand poly-(N- carblnol) derivatives of the amlnotriazoles, of the aminodiazines, etc. Particularly good results are obtained with active methylene-containing bodies such as a methylol urea, more particularly monoand dimethylol areas, and a methyloi melamine, e. g., monomethylol melamine and poiymethyloi melamines (di-, tri-, tetra-, penta-, and hexamethylol melamines). Mixtures of aldehydes and aldehyde-addition products may b employed, e. g., mixtures 01 formaldehyde and methylol compounds such, for instance, as dimethyioi urea, trimethylol melamine, hexamethylol melamine, etc.

The ratio 01 the aldehydic reactant to the triauine derivative may be varied over a wide range depending, for example, upon the particular properties desired in the finished product. Ordinarily these reactants are employed in an amount corresponding to at least one mol of the aldehyde, specifically formaldehyde, for each moi oi the triazine derivative. Thus, we may use, for example, from 1 to 8 or 9 or more mols of an aidehyde for each mol of the triazine derivative. When the aldehyde is available tor reaction in the form oi! an aikylol derivative, more particularly a methylol derivative such, for instance, as dimethylol urea, trimethyloi melamine, etc., then higher amounts of such aldehyde-addition prodaseascc acts are used, for instance from 2 or 3 up to 15 or 20 or more mols 0! such alkylel derivatives for each mol of the triazine derivative.

As indicated hereinbefore, and as further shown by a number of the examples, the properties of the fundamental resins of this inventio may be varied widely by introducing other modifying bodies beiore, during or after eilfecting condensation between the primary components. Thus, as modifying agents we may use, for example, methyl, ethyl, propyi, isopropyl, isobutyl, hexyl, etc., monohydric alcohols; polyhydric alcohols such, for example, as diethylene glycol, triethylene glycol, pentaerythritoi, etc.; alcohol-others, e. g., ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monohutyl ether, diethyiene glycol monomethyl ether, diethylene glycol monoethyi ether, diethyiene glycol monobutyl ether, etc.; amides such as tormamide, stearamide, acrylamide, benzene sulionamides,, toluene sulionamides, adipic dlamide, phthalamide, etc.; amines, e. g., ethylene diamine, phenyiene diamine, etc. ketones, including halogenated ketones; nitriles, including halogenated nitriles, e. g., acryionitrile, methacryionitriie, succinonitrile, chloroacetonltriles, etc.; acylated ureas, more particularly halogenated acylated ureas oi the kind described, for example, in DAlelio Patent No. 2,281,559; and others.

The modifying bodies also may take the form of high molecular weight bodies with or without resinous characteristics, for example, hydrolyzed wood products, formalized cellulose derivatives, lignin, protein-aldehyde condensation products, aminodiazine-aldehyde condensation products, aminotriazole-aldehyde condensation products, melamine-aldehyde condensation products, etc. Other examples of modifying bodies are the ureaaldehyde condensation products, the aniline-aldehyde condensation products, iuriurai condensation products, phenol-aldehyde condensation products, modified or unmodified, saturated or unsaturated polyhydric alcohol-polycarboxylic acid condensation products, water-soluble cellulose derivatives, natural gums and resins such as shellac, rosin, etc.; polyvinyl compounds such as polyvinyl esters, e. g., polyvinyl acetate, polyvinyl butyrate, etc., p lyvinyl others, including polyvinyl acetals, specifically polyvinyl formal, etc.

Dyes, pigments, plasticizers, mold lubricants, opacifiers and various fillers (e. g., wood flour, glass fibers, asbestos, including defibrated asbestos, mineral wool, mica, cloth cuttings, etc.) may be compounded with the resin in accordance with conventional practice to provide various thermoplastic and thermosetting molding compositions.

The modified and unmodified resinous compositions of this invention have a wide variety of uses. For example, in addition to their use in the Production of molding compositions, they may be used as modifiers of other natural and synthetic resins, as laminating varnishes in the production of laminated articles wherein sheet materials, e. g., paper, cloth, sheet asbestos, etc., are coated and impregnated with the resin, superimposed and thereafter united under heat and pressure. They may be used in the production 01 wire or baking enamels from which insulated wires and other coated products are made, for bonding together mica flakes in the production of resin-bonded abrasive articles such, for instance, as grind stones, sandpapers. etc., in the manufacture of electrical resistors, etc. They also may be employed for treating cotton, linen and other cellulosic materials in sheet or other form. They also asoasos maybeusedasimpregnants foreleotricalooihsnd for other electrically insulating applications.

Whatweclalmasnewanddesiretosecumby Letters Patent of the United States is:

i. A composition of matter comprising the reaction product of ingredients comprising an aidehyde andacompoundcorrespondingtothsgeneral formula mil 1/ lime... Livia-l g where n represents an integer and is at least i andnotmorethan3.itrepresentsamembcrof the class consisting of hydrogen and monovaient hydrocarbon and halo-hydrocarbon radicals, and R representsamemberoftheclassconsistingof monovalent aliphati hydrocarbon radicals and so 8. A heat-curable resinous composition comproductofmactionofingredientsincludinganaldehydeandacorrespondingtothegeneraliormula where R represents a member of the class consisting of monovalent aliphatic hydrocarbon radicals and monovalent aromatic and nuclearly halogenated aromatic hydrocarbon radicals.

13. A resinous composition comprising the condensation product of ingredients comprising di- (aeetylhydrazino) amino s-triaslne and formaldehyde.

14. A composition comprising the product of reaction of ingredients comprising a urea. an aidehyde and a compound corresponding to the general formula 0 (arm L i it NH-NR-i'J-B') where n represents an integer and is at least i and not more than 3, R represents a member of the class consisting of hydrogen and monovalent hydrocarbon and halo-hydrocarbon radicals. and R represents a member of the class consisting of mqnovalent aliphatic hydrocarbon radicals and monovalent aromatic and nuclear-1y halogenated aromatic hydrocarbon radicals.

15. A composition as in claim 14 wherein R.

represents hydrog n, the aldehyde is formalde- Prmng heahmmuble mama product: hyde and the urea component is the compound of ingredients including formaldehyde and a com; pound correponding to the general formula where n represents an integer and is at least i and not more than 3, and It represents a member of the class consisting of monovalent aliphatic hydrocarbon radicals and monovalent aromatic and nuclearly halogenated aromatic hydrocarbon radicals.

9. A product comprising the cured composition of claim 8.

10. A composition comprising the resinous product of reaction of ingredients including an aldehyde and a compound corresponding to the general formula where it represents a member of the clue consisting of monovalent aliphatic hydrocarbon radicais and monovalent aromatic and nuclearly halogenated aromatic hydrocarbon radicals.

ii. A resinous composition comprising the condensation product of ingredients comprising an aoetylhydrazino diamino s-trlazine and formalde y e.

12. A composition comprising the resinous HrN- ' corresponding to the formula mm.

16. A resinous composition comprising the product of reaction of ingredients comprising urea, formaldehyde and aceiylhydrasino diamino s-trlazine.

17. A composition comprising the product of re. action of ingredients comprising melamine, an aldehyde and a compound corresponding to the general formula where n represents an integer and is at least 1 and not more than 3, R represents a member of the class consisting of hydrogen and monovalent hydrocarbon and halo-hydrocarbon radicals. and R represents a member of the class consisting of monovalent aliphatic hydrocarbon radicals and where it represents a member of the class consistingofmonovaientaliphatichydrocarbonradcals and monovalent aromatic and nuclearly halogenated aromatic hydrocarbon radicals.

19. A heat-curable composition comprising the heat-convertible resinous reaction product of (l) a product of partial reaction of ingredient ineluding formaldehyde and a compound corresponding to the general formula N o t c-nn-rm- -a' where R. represents a member at the class consisting of monovalent aliphatic hydrocarbon radicals and monovalent aromatic and nuclearly halogenated aromatic hydrocarbon radicals, and (2) a curing reactant.

20. The method of preparing new synthetic compositions which comprises efl'ecting reaction between ingredients comprising an aldehyde and a compound corresponding to the general formula where n represents an integer and is at least 1 and not more than 3, R. represents a member or the class consisting of hydrogen and monovalent hydrocarbon and halo-hydrocarbon radicals, and R represents a member of the class consisting of monovalent aliphatic hydrocarbon radicals and monovalent aromatic and nuclearly halogenated aromatic hydrocarbon radicals.

21. A composition comprising the resinous reaction product or (1) a chlorinated acetamide and (2) a product of partial reaction of ingredients including formaldehyde and a compound Certificate of Correction Patent No. 2,392,366.

January 8, 1946.

GAETANO F. DALELIO ET AL.

It is hereby certified that errors appear in the printed s eeification of the above numbered patent requiring correction as follows: Page 1,

rst column, line 51, for

or before halogeno-substituted read of; and second column, lines 29 and 30, for aeylhydrazino read carboacylhydrazino; page 4, first column, line 68, for sulfanic read s-ulfamw; page 7, second column, line 5, for that portion of the formula reading N l\ f read NH ;.and that the said Letters Patent should be read with these corrections therein that the same may conform to the record of the case in the Patent Office.

Signed and sealed this 11th day of June, A. D. 1946.

[cut] LESLIE FRAZER,

First Assistant Commissioner of Patents.

cals and monovalent aromatic and nuclearly halogenated aromatic hydrocarbon radicals.

19. A heat-curable composition comprising the heat-convertible resinous reaction product of (l) a product of partial reaction of ingredient ineluding formaldehyde and a compound corresponding to the general formula N o t c-nn-rm- -a' where R. represents a member at the class consisting of monovalent aliphatic hydrocarbon radicals and monovalent aromatic and nuclearly halogenated aromatic hydrocarbon radicals, and (2) a curing reactant.

20. The method of preparing new synthetic compositions which comprises efl'ecting reaction between ingredients comprising an aldehyde and a compound corresponding to the general formula where n represents an integer and is at least 1 and not more than 3, R. represents a member or the class consisting of hydrogen and monovalent hydrocarbon and halo-hydrocarbon radicals, and R represents a member of the class consisting of monovalent aliphatic hydrocarbon radicals and monovalent aromatic and nuclearly halogenated aromatic hydrocarbon radicals.

21. A composition comprising the resinous reaction product or (1) a chlorinated acetamide and (2) a product of partial reaction of ingredients including formaldehyde and a compound Certificate of Correction Patent No. 2,392,366.

January 8, 1946.

GAETANO F. DALELIO ET AL.

It is hereby certified that errors appear in the printed s eeification of the above numbered patent requiring correction as follows: Page 1,

rst column, line 51, for

or before halogeno-substituted read of; and second column, lines 29 and 30, for aeylhydrazino read carboacylhydrazino; page 4, first column, line 68, for sulfanic read s-ulfamw; page 7, second column, line 5, for that portion of the formula reading N l\ f read NH ;.and that the said Letters Patent should be read with these corrections therein that the same may conform to the record of the case in the Patent Office.

Signed and sealed this 11th day of June, A. D. 1946.

[cut] LESLIE FRAZER,

First Assistant Commissioner of Patents. 

